Flame and smoke retardant vinyl chloride and vinylidene chloride polymer compositions

ABSTRACT

Flame and smoke retardant vinyl chloride and vinylidene chloride polymer compositions are obtained by including therein a compound selected from the group consisting of AlB12, Cr2S3, Cu3N, Cu2S, CuS, FeS, MoB2, SnS2, TiB2 and mixtures thereof.

United States Patent Kroenke 51 May 13, 1975 FLAME AND SMOKE RETARDANT VINYL CHLORIDE AND VINYLIDENE CHLORIDE POLYMER COMPOSITIONS William J. Kroenke, Brecksville, Ohio The B. F. Goodrich Company, Akron, Ohio Filed: Feb. 1, 1974 Appl. No.: 438,724

Inventor:

Assignee:

U.S. Cl.260/45.75 F; 260/457 R; 260/4575 R;

260/4575 A; 260/4575 P; 260/4575 G; 260/4575 C Int. Cl. C08f 45/56 Field of Search 260/4575 R, 42.41, 42.49, 260/45] R; 117/138 Primary ExaminerV. P. Hoke Attorney, Agent, or FirmJ. Hughes Powell, Jr.

[57] ABSTRACT Flame and smoke retardant vinyl chloride and vinylidene chloride polymer compositions are obtained by including therein a compound selected from the group consisting of MB Cr S Cu N, Cu S, CuS, FeS, MoB SnS TiB and mixtures thereof.

8 Claims, No Drawings FLAME AND SMOKE RETARDANT VINYL CHLORIDE AND VINYLIDENE CHLORIDE POLYMER COMPOSITIONS BACKGROUND OF THE INVENTION Vinyl chloride and vinylidene chloride polymers are known to be self-extinguishing and relatively more flame retardant than other polymers such as polyethylene, polypropylene and the like. However, smoke may be produced upon exposure of vinyl chloride and vinylidene chloride polymers to a flame. In addition, improved flame retardancy of these polymers may be desired for applications such as aircraft interiors and the like. Conventional flame retardants such as antimony oxide do not aid in smoke reduction. New vinyl chloride and vinylidene chloride polymer compositions are desired which are capable of both flame retardation and smoke reduction.

SUMMARY OF THE INVENTION Flame and smoke retardant vinyl chloride and vinylidene chloride polymer compositions are obtained by including therein a compound selected from the group consisting of Alb Cr S Cu N, Cu S, CuS, FeS, M08 SnS TiB and mixtures thereof.

DETAILED DESCRIPTION Vinyl chloride and vinylidene chloride polymers used in this invention include homopolymers, copolymers and blends of homopolymers and/or copolymers. The vinyl chloride and vinylidene chloride polymers may contain from up to about 50% by weight of at least one other vinylidene monomer (Le, a monomer containing at least one terminal CH C group per molecule) copolymerized therewith, more preferably up to about 20% by weight of such monomer. These monomers include l-olefins having from 2 to 12 carbon atoms, more preferably from 2 to 8 carbon atoms, such as ethylene, propylene, l-butene, isobutylene, l-hexene, 4-methyl-l-pentene and the like;

dyl methacrylate and the like, and including esters of maleic and fumaric acid and the like; amides of the a,B-olefinically unsaturated carboxylic acids such as acrylamide and the like; divinyls, diacrylates and other polyfunctional monomers such as divinyl benzene, divinyl ether, diethylene glycol diacrylate, ethylene glycol dimethacrylate, methylene-bis-acrylamide, allyl pentaerythritol, and the like; bis(B-haloalkyl) alkenyl phosphonates such as bis(B-chloroethyl) vinyl phosphonate and the like; and the like.

More preferred monomers include l-olefins having from 2 to 12 carbon atoms, more preferably from 2 to 8 carbon atoms, such as ethylene, propylene, l-butene, isobutylene, l-hexene, 4-methyl-l-pentene and the like; vinyl esters and allyl esters such as vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl laurate, allyl acetate and the like; olefinically unsaturated carboxylic acids and esters thereof, including a,B-olefinically unsaturated acids and esters thereof such as methyl acrylate, ethyl acrylate, chloropropyl acrylate, butyl acrylate, hexyl acrylate, Z-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, cyclohexyl acrylate, phenyl acrylate, glycidyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, hexylthioacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate and the like, and including esters of maleic and fumaric acid and the like; and amides of a ti-olefinically unsaturated carboxylic acids such as acrylamide and the like.

The additive compounds or mixtures thereof used in this invention are polycrystalline or amorphous materials selected from the group consisting of MB 12 Cr2S CllgN, Cu S, CuS, FeS, MOBz, SnS2, TiB and mixdienes having from 4 to 10 carbon atoms including such conjugated dienes as butadiene, isoprene, piperylene and the like; ethylidene norbornene and dicyclopentadiene; vinyl esters and allyl esters such as vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl laurate, allyl acetate and the like; vinyl aromatics such as styrene, a-methyl styrene, chlorostyrene, vinyl toluene, vinyl naphthalene and the like; vinyl and allyl ethers and ketones such as vinyl methyl ether, allyl methyl ether, vinyl isobutyl ether, vinyl n-butyl ether, vinyl chloroethyl ether, methyl vinyl ketone and the like;

vinyl nitriles such as acrylonitrile, methacrylonitrile.

about microns to about 0.5 micron, more preferably about 40 microns to about 0.5 micron. Acicular single crystals (whiskers) are not desired because they disperse less readily and are substantially more expensive. The additives used in this invention are all colored compounds. Polymer compositions containing them may have colors similar to, although somewhat lighter than the compounds themselves.

The additive compounds are used in amounts from about 0.25 to about 10 parts by weight per 100 parts -by weight of polymer. The amount used may be varied to obtain a proper balance of flame retardancy and smoke retardancy. Use of more than about 10 parts by weight of additive per 100 parts by weight of polymer probably will affect adversely other important physical properties, such as tensile strength and the like. Preferred approximate concentration ranges of additives for improving the important flammability characteristics are summarized in Table I:

TABLE l-Continued Preferred Flammability Concentration Characteristic Additive Range (PHR) do. Cr S ,Cu,-,N 0.5 10

do. M08 0.5

do. FeS l 10 do. TiB 2 10 The vinyl chloride and vinylidene chloride polymers may be prepared by any method known to the art such as by emulsion, suspension, bulk or solution polymerization. The additive compounds may be mixed with the polymer emulsion, suspension, solution or bulk mass before monomer recovery and/or drying. More preferably the compounds may be mixed with dry granular or powdered vinyl halide polymers. The polymer and compound may be mixed thoroughly in granular or powder form in apparatus such as a Henschel mixer and the like. Alternatively, this step may be eliminated and the mixing done while the polymer mass is fluxed, fused and masticated to homogeneity under fairly intensive shear in or on a mixer apparatus having its metal surface in contact with the material. The fusion temperature and time will vary according to the polymer composition and level of additive compound but will generally be in the range of about 300 to 400F and 2 to 10 minutes.

Flame and smoke retardancy may be measured using the Goodrich Smoke OI Test. The test results correlate well to the Oxygen Index (ASTM D2863-70). The

93 BC actual char-expected nonburnable residues for the point on the mass loss rate curve where m is a constant (0.6 grams/min.). Suitable flame and smoke retardant compositions have substantially higher Goodrich Ol numbers and lower Goodrich smoke numbers than control samples.

Smoke retardancy and char enhancement may be measured quickly using the Goodrich Smoke-Char Test. Small (0.3-0.4g) polymer samples measuring about V2 in. X in. X 0.075 in. are placed on a screen and burned with a propane gas flame rising vertically from beneath the sample. Sample geometry at a constant weight has been found not to be significant for the small samples used in this test. A Bernz-O-Matic pencil flame burner head is used with gas pressure maintained at psig. The sample is immersed totally and continuously in the flame. Smoke from the burning sample rises in a vertical chimney and passes through the light beam of a Model 407 Precision Wideband Photometer (Grace Electronics, Inc., Cleveland, Ohio.) coupled with a Newport photometer integrator. Other integrating spectrophotometers also may be used. The smoke number, S is a measurement of smoke generation as integrated area per gram of polymer in the sample compound.

The residue or char remaining after the Goodrich Smoke-Char Test is weighed and used to calculate the percent of backbone char (%BC), which takes into account nonburnable residues identified, for example, by X-ray diffraction analysis. BC is, therefore, a measurement of polymer resistance to burning. The following formula is used to calculate percent of backbone char from the indicated variable weights:

compound i-rt.-nonPVC ingredients-HQl e ontent test results also correlate to NBS Smoke Chamber data (ASTM ST? 422, pp.l66204) over the full NBS Smoke Chamber test range. Generally in. X 6 in. X 0.075 in. strips are used for testing rigid polymers and /s in. X 6 in. X M1 in. strips for plasticized polymers. The Goodrich Smoke IO testing is performed in a standard Oxygen Index test chamber (described in ASTM D2863-70) modified to permit the smoke from the burning samples to rise in the vertical chimney and pass through the light beam of an integrating spectrophotometer. The integrated area provides a measure of the amount of smoke generated by a burning sample.

Mass loss rates (m grams/minute) for the Goodrich Smoke -Ol Test are determined at five or more different oxygen concentrations and plotted against these concentrations. Linear regression analysis is used to find the mass loss rate curve that best fits the data; correlation coefficients are at least 0.90 and generally about 0.95. The Goodrich Ol number is the oxygen concentration at which m 0.3 grams/minute. Successive tests of a given composition have a reproducibility of about i 1% oxygen. A Goodrich smoke number (D l/cm) is calculated using the formula where PVC is used to designate vinyl chloride and vinylidene chloride polymers.

The vinyl chloride and vinylidene chloride polymer compositions of this invention may contain the usual compounding ingredients known to the art such as fillers, stabilizers, opacifiers, lubricants, processing aids, impact modifying resins, plasticizers, antioxidants and the like.

The improved flame and smoke retardant vinyl chloride and vinylidene chloride compositions of this invention are useful wherever flame and smoke resistance are desirable, such as in plastic components for airplane interiors, childrens toys, house siding and the like. Of course, overall suitability for a particular use will depend upon other factors as well, such as comonomer type and level, compounding ingredient type EXAMPLE 1 The following recipe was used:

mass loss rate (grams/min.)

MATERIAL PARTS Polyvinyl Chloride (1) 100 Polyethylene Powder Processing Aid 2 Dibutyl tin bis(isooctylthioglycollate) Stabilizer 2 Additive (2) (l) I-lomopolymer having an inherent viscosity about 0.94 0.99; ASTM classification GP-4l5443.

(2) Additive selected from A|B,,.cr,s,, Cu N,Cu S.CuS,FeS,MoB .SnS, and TiB The control sample contained no additive.

Each experimental sample was prepared by blending the above materials using an Osterizer blender. The dibutyl tin bis(isooctylthioglycollate) was added in four 0.5g portions to the other materials, with second intervals between each addition. The samples were then milled on a two-roll mill for about 3 minutes at a roll surface temperature of about 320F. The milled samples were pressed into 6 X 6 X 0.075 in. sheets at about 330F using 40,000 lbs. of force applied to a 4-in. ram. The samples were given a 3-minute preheat prior to pressing for 6 minutes under full load.

The molded samples were cut into 4 X 6 X 0.075 in. strips and tested using the Oxygen Index (ASTM D286370) and Goodrich Smoke-OI tests described heretofore. Test results are given in Table 11:

01 at m 0.3g/min.

" D at m 0.6g/min.

These results demonstrate that the additives above substantially retard flame and smoke during burning of rigid polyvinyl chloride in the oxygen-enriched atmosphere used for the ASTM D2863-70 Oxygen Index and Goodrich Smoke 01 tests.

EXAMPLE 2 The following recipe was used:

MATERIAL PARTS Polyvinyl Chloride (1) 100 Polyethylene Powder Processing Aid 2 Dibutyl tin bis(isooctylthioglycollate) stabilizer 2 Additive (2) Variable (l) Homopolymer having an inherent viscosity of about 0.94-0.99; ASTM Classification GP-4-l5443 (2) Additive selected from AlB Cfgsa, Cu N,Cu S,CuS,FeS,MoB,, SnS, and TiB The control sample contained no additive.

Each experimental sample was prepared by blending the above materials using an Osterizer blender. The dibutyl tin bis(isooctylthioglycollate) was added in four 0.5g portions to the other materials, with 15 second intervals between each addition. The samples were then milled on a two-roll mill for about 3 minutes at a roll surface temperature of about 320F. The milled samples were pressed into 6 X 6 X 0.075 in. sheets at about 330F using 40,000 lbs. of force applied to a 4-in. ram. The samples were given a 3-minute preheat prior to pressing for 6 minutes under full load.

The molded samples were cut into 0.3 0.4 gram samples (about X X 0.075 in.) and tested using the Goodrich Smoke-Char Test described heretofore. Tests results are given in Table 111.

TABLE III Additive Smoke Formation Char Formation Type PHR* S BC*** Reduction Increase None 112 2.72

AlB 10 87 22 0 0 Cr s l 11 13.5 397 Cr S: 10 84 25 19.5 616 Cu N 10 63 44 39.3 134 Cu S l 69 38 21.4 689 Cu S 5 69 38 17.2 531 Cu S 10 67 40 20.4 648 CuS l 67 40 24.7 810 CuS 10 55 51 25.1 823 FeS 10 97 13 32.3 1090 MOB; 1 79 29 41.1 1410 MOB, 10 123 0 0 0 SnS 1 71 37 28.2 938 SnS, 10 59 47 30.8 1030 TiB, 2 109 1 8.6 218 TiB 10 62 45 10.4 281 Weight parts of additive per 100 weight parts of polyvinyl chloride. Lower S, indicates less smoke formation. Backbone Char discussed heretofore at p. 7.

These results demonstrate that the defined additives substantially reduce smoke evolution and enhance char formation during forced burning of rigid polyvinyl chloride in the Goodrich Smoke-Char test.

I claim:

1. A flame and smoke retardant composition comprising (1) a vinyl chloride or vinylidene chloride polymer and (2) a compound selected from the group consisting of A18 MoB TiB and mixtures thereof, said compound being present in an amount of from about 0.25 to about 10 weight parts per 100 weight parts of polymer and having an average particle size of from about 100 microns to about 0.5 micron.

2. A composition of claim 1 wherein said polymer contains copolymerized therewith up to about 50% by 'weight of at least one other vinylidene monomer containing at least one terminal group per molecule.

3. A composition of claim 2 wherein said polymer contains copolymerized therewith up to about 20% by weight of said other vinylidene monomer.

4. A composition of claim 3 wherein said other vinylidine monomer is selected from the group consisting of l-olefins having from 2 to 12 carbon atoms, vinyl esters, a,B-olefinica1ly unsaturated carboxylic acids and esters thereof, amides of a,fi-olefinically unsaturated carboxylic acids, and esters of fumaric and maleic acid.

5. A composition of claim 4 wherein said compound has an average particle size of from about 40 microns to about 0.5 micron.

6. A composition of claim 5 wherein said compound IS AIBn.

7. A composition of claim 5 wherein said compound is M03 8. A composition of claim 5 wherein said compound is TIBg. 

1. A FLAME AND SMOKE RETARDANT COMPOSITION COMPRISING (1) A VINYL CHLORIDE OR VINYLIDENE CHLORIDE POLYMER AND (2) A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALB12, MOB2, TIB2 AND MIXTURE THEREOF, SAID COMPOUND BEING PRESENT IN AN AMOUNT OF FROM ABOUT 0.25 TO ABOUT 10 WEIGHT PARTS PER 100 WEIGHT PARTS OF POLYMER AND HAVING AN AVERAGE PARTICLE SIZE OF FROM ABOUT 100 MICRONS TO ABOUT 0.5 MICRON.
 2. A composition of claim 1 wherein said polymer contains copolymerized therewith up to about 50% by weight of at least one other vinylidene monomer containing at least one terminal
 3. A composition of claim 2 wherein said polymer contains copolymerized therewith up to about 20% by weight of said other vinylidene monomer.
 4. A composition of claim 3 wherein said other vinylidine monomer is selected from the group consisting of 1-olefins having from 2 to 12 carbon atoms, vinyl esters, Alpha , Beta -olefinically unsaturated carboxylic acids and esters thereof, amides of Alpha , Beta -olefinically unsaturated carboxylic acids, and esters of fumaric and maleic acid.
 5. A composition of claim 4 wherein said compound has an average particle size of from about 40 microns to about 0.5 micron.
 6. A composition of claim 5 wherein said compound is AlB12.
 7. A composition of claim 5 wherein said compound is MoB2.
 8. A composition of claim 5 wHerein said compound is TiB2. 